Polyamines and polymers made therewith

ABSTRACT

A polyamine having the formula: 
     
       
         H 2 N—A[NR—B] a NH 2   
       
     
     or salt thereof, wherein A and B, which may be the same or different, are selected from aliphatic or aromatic substituents provided that at least four carbon atoms separate any two nitrogen groups, R is an aliphatic or aromatic group, and a is 2 to 5. In addition, a polymer having the formula:                    
     or salt thereof, wherein A, B and Q, which may be the same or different, are selected from aliphatic or aromatic substituents provided that at least four carbon atoms separate any two nitrogen groups, R is an aliphatic or aromatic group, a is greater than 1 to about 5, and n is 3 to about 1,000. The polymers are useful for improving acid-dyeability of polymer compositions, fibers, fabrics, films and other articles.

PRIORITY

This application claims priority from and is a divisional of U.S. patentapplication Ser. No. 09/938,696, filed Aug. 24, 2001, now U.S. Pat. No.6,713,653 incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to polyamines and polymers made therewithsuitable for use in manufacturing fibers, fabrics, films and otheruseful articles, and to the articles and methods of making suchcompositions and articles. This invention also relates to processes forpreparing the polyamines and polymers and use thereof, includingacid-dyeable polymer compositions made with the polymers.

BACKGROUND OF THE INVENTION

Polyesters, especially polyalkylene terephthalates, have excellentphysical and chemical properties and have been widely used for resins,films and fibers. In particular, polyester fibers have a high meltingpoint, and can attain high orientation and crystallinity. Accordingly,polyesters have excellent fiber properties such as chemical, heat andlight stability, and high strength. However, polyesters, especiallypolyester fibers and fabrics, are difficult to dye. The molecularstructure and the high levels of orientation and crystallinity thatimpart the desirable properties to the polyester also contribute to aresistance to coloration by dye compounds. Also contributing to thedifficulty in dyeing polyester compositions is the characteristic thatpolyesters do not have dye sites within the polymer chain that arereactive to basic or acid dye compounds.

Nylon polymers are generally dyed more easily than polyesters because oftheir greater permeability and, in the case of the preferred acid dyes,because the amine end groups in nylon serve as dyesites. However, inmany cases these amine-end dyesites are not present at sufficiently highconcentration to give the desired depth of dyeing, particularly infine-denier fibers. Therefore, improvements in the acid dyeability ofnylon are desired.

To impart acid dyeability to polyester, it has been proposed to blendpolyester with nylon 6 or nylon 6,6 to obtain the benefits of theamine-end dyesites in the resulting polyester/polyamide copolymercomposition. The high concentrations of polyamide that may be requiredto impart dyeability in this polyester/polyamide composition can resultin forming polyamide microfibrils, which decrease the physicalproperties of the polyester/polyamide copolymer and create difficultiesin processing.

Co-polymerizing nitrogen containing compounds into polyester chains toimprove acid dyeability has been disclosed in, for instance, U.S. Pat.Nos. 3,901,853, 4,001,189 and 4,001,190.

Canadian Patent No. 974,340 discloses acid-dyeable polyestercompositions comprising tertiary nitrogen-containing polyamides.Preferred are copolyamides of two or more monomers inclusive ofdiamines, dicarboxylic acids and aminocarboxylic acids. The tertiarynitrogen component may be derived from piperazine derivatives;HOOC(—CH₂)_(n)—NR—(CH₂)_(n)—COOH, wherein R can be a group selected fromthe class consisting of aliphatic (branched or unbranched),cycloaliphatic, aryl or heterocyclic groups; R₁—NH—R₂—NR₃—R₄—NHR₅,wherein R₂ and R₄ can be a group selected from aliphatic (branched orunbranched), cycloaliphatic or aryl, R₁ and R₅ can be a group selectedfrom hydrogen, aliphatic (branched or unbranched), cycloaliphatic oraryl, and R₃ is aliphatic (branched or unbranched), cycloaliphatic, arylor heterocyclic; and cyclic polyamines. Piperazine ring containingpolyamides are preferred and all of the examples are directed to thesecompounds, and to their use with polyethylene terephthalate orpolybutylene terephthalate. Piperazine ring containing polyamides, acyclic compound containing two nitrogens on a single ring, is notsufficiently thermally stable for many applications.

WO 01/34693 (corresponding to co-pending U.S. patent application Ser.No. 09/708,209, filed Aug. 11, 2000 (Docket No. RD-7850)), discloses anacid-dyeable polyester composition made by melt-blending a polyesterwith a polymeric additive containing a secondary amine salt or asecondary amine, such as made by combining bis(hexamethylene)triaminewith a second monomer unit such as a terephthalate. This technology isparticularly useful for dyeing fabrics lightly, but adding 3-4 mole % ormore of the dye has been found to impact physical properties,particularly tenacity. Tenacity is improved by adding phosphorous acid;however, phosphorous acid leads to instability of pack pressure and maycause spin problems over the long run. In addition, it was not possibleto significantly increase the amount of BHMT added using phosphorus acidwithout spin problems. Therefore, an additive that can provide deepdyeable polyester with acid dyes without such drawbacks is desired.

U.S. Pat. No. 5,000,792 discloses a pigment dispersing agent comprisingthe polyester reaction product of a polyester having a free carboxylgroup, of which the acid value is in the range of from 10 to 60, with anamine compound of the formula: NH₂—R₁—(NR₃)—R₂—NH₂ wherein R₁ and R₂ arealkylene radicals which can be the same or different, each containing 2to 6 carbon atoms, and R₃ is a radical of the formula CH₃— or C₂H₅—. Thedispersing agent is used to disperse pigments in paints and inks.

All of the aforementioned documents are incorporated herein byreference.

It is desirable to have acid-dyeable nitrogen-containing polymercompositions, particularly polyester and/or nylon compositions, withgood physical properties which may be easily processed into fibers,films or other shaped articles and acid-dyed without expensiveadditives, special solutions, spinning problems, and/or complicatedapplication procedures. It is particularly desirable to be able to deepdye such compositions or shaped articles.

SUMMARY OF THE INVENTION

This invention is directed to a polyamine having the formula:

H₂N—A[NR—B]_(a)NH₂

or salts thereof, wherein A and B, which may be the same or different,are selected from aliphatic or aromatic substituents provided that atleast four carbon atoms separate any two nitrogen groups, R is analiphatic or aromatic group, and a is 2 to 5.

In one preferred embodiment the polyamine is a salt and in another it isnot a salt. Preferred salts are acid salts. The polyamine is preferablysalinized with phosphorous acid, phosphoric acid, pyrophosphoric acid orphenyl phosphinic acid.

In a preferred embodiment, a is 2.

In a preferred embodiment, the polyamine is:

H₂N(CH₂)_(x)[NR(CH₂)_(y)]_(a)NH₂

or salt thereof, wherein x and y, which may be the same or different,are 4 to 10, a is 2 to 5, and R is an alkyl group containing 1 to 8carbons in a straight or branched chain. In one preferred embodiment, ais 2. In one preferred embodiment the polyamine is a salt and in anotherit is not a salt.

One preferred polyamine is dimethyltributylenetetramine. One preferredpolyamine salt is the phosphorous salt of dimethyltributylenetetramine.

The invention is also directed to polymers having the formula:

or salts thereof, wherein A, B and Q, which may be the same ordifferent, are selected from aliphatic or aromatic substituents providedthat at least four carbon atoms separate any two nitrogen groups, R isan aliphatic or aromatic group, a is greater than 1 to about 5, and n is3 to about 1,000. Preferably, a is about 2 to about 5.

In one preferred embodiment the polymer is a salt and in another it isnot a salt. Preferred salts are acid salts. The polymer is preferablysalinized with phosphorous acid, phosphoric acid, pyrophosphoric acid orphenyl phosphinic acid.

Preferably, n is from 3 to about 100, more preferably n is from 3 toabout 20.

Preferably, A, B and Q are selected from alkylene substituentscontaining from 4 to 20 carbons and arylene substituents containing from6 to 18 carbons. More preferably, R is C₁-C₈ alkyl, and A and B areC₄-C₈ alkylene and Q is C₄-C₁₀ alkylene.

In a preferred embodiment, the polymer is prepared by polymerizing (a)polyamine having the formula:

H₂N(CH₂)_(x)[NR(CH₂)_(y)]_(a)NH₂

or salts thereof, wherein x and y, which may be the same or different,are 4 to 10, a is 2 to 5, and R is an alkyl group containing 1 to 8carbons in a straight or branched chain and (b) aliphatic and aromaticdicarboxylic acids or esters, such as adipic acid, dimethyl adipate,terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethylisophthalate, naphthalene dicarboxylic acid, dimethyl naphthalenedicarboxylate, or mixtures thereof. Preferred are adipic acid, dimethyladipate, terephthalic acid, dimethyl terephthalate and mixtures thereof.

The polymers of this invention are useful in preparing acid-dyeablepolymer compositions, and in this context, in the following sections ofthis document are referred to as “polymeric additive(s)” or “polymercompound(s)” and the other polymers, such as nylon or polyester arereferred to as the “polymer(s).” Such an acid-dyeable polymer comprises(a) polymer (e.g., nylon or polyester) and (b) the polymeric additive.

Preferred polymers are nylons and polyesters.

Nylon is acid-dyeable and the invention makes it possible to deep-dyenylon or tailor nylons to achieve desired colors. For instance, withthis invention it is possible to prepare nylon compositions, fibers andother products which can be dyed to a deep shade. The invention isparticularly useful with nylon 6, nylon 4,6, nylon 6,6, nylon 6,10,nylon 6,12, nylon 12,12 and copolymers thereof, and blends thereof.

The composition can be prepared by melt blending the polymer and thepolymeric additive. The polymeric additive is added so that the amountof tertiary amine units is effective to promote acid-dyeability. Suchcompositions are useful in forming fibers, including monocomponent andmulticomponent (e.g., bicomponent) fibers. For instance, it may be usedas one or both component of a bicomponent fiber comprising poly(ethyleneterephthalate) and poly(trimethylene terephthalate) components. Thecomposition can also be used as a film or film layer.

The composition or products made therewith (e.g., fibers or films) canbe acid dyed.

DETAILED DESCRIPTION OF THE INVENTION

By “acid-dyeable” it is meant that the composition itself, or fiber,fabric, film or any other article (e.g., shaped articles) made with thecomposition has an affinity for acid dyes.

The polymer composition preferably comprises either polyesters ornylons, or blends of one or more of these.

Reference to a polymer should be understood to mean a single polymer orblends or mixtures of such a polymer. In other words, “polyester” meansone or more polyesters. Thus, for instance, if applicant refers to acomposition containing x mole % of a polyester, the composition maycomprise x mole % of one polyester or x mole % total of differentpolyesters. Similarly, “polymeric additive” means one or more polymericadditives.

One preferred class of polymers is polyesters. By “polyester” or “apolyester”, applicant is referring to a single polyester, and/or toblends or mixtures of polyesters. The preferred polyesters arepolyalkylene terephthalates, polyalkylene naphthalates and polyalkyleneisophthalates, and polyalkylene terephthalates are most preferred. Morepreferred are polyethylene terephthalates, polytrimethyleneterephthalates and polytetramethylene terephthalates.

The Mn for the polyester (e.g., polyalkylene terephthalate) ispreferably at least about 15,000, more preferably at least about 18,000,and is preferably about 40,000 or less, more preferably about 35,000 orless. The preferred Mn depends on the polyester used.

In the absence of an indication to the contrary, a reference topolyester is intended to include reference to copolyesters. Forinstance, reference to “polyalkylene terephthalate” is meant also toencompass copolyesters, i.e., polyesters made using 3 or more reactants,each having two ester forming groups. For example, a copoly(ethyleneterephthalate) can be used in which the comonomer used to make thecopolyester is selected from the group consisting of linear, cyclic, andbranched aliphatic dicarboxylic acids having 4 to 12 carbon atoms (forexample butanedioic acid, pentanedioic acid, hexanedioic acid,dodecanedioic acid, and 1,4-cyclo-hexanedicarboxylic acid); aromaticdicarboxylic acids other than terephthalic acid and having 8-14 carbonatoms (for example, isophthalic acid and 2,6-naphthalenedicarboxylicacid); and from linear, cyclic, and branched aliphatic diols having 3-8carbon atoms (for example, 1,3-propanediol, 1,2-propanediol,1,4-butanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol,2-methyl-1,3-propanediol, and 1,4-cyclohexanediol); and aliphatic andaromatic ether glycols having 4-10 carbon atoms (for example,hydroquinone bis(2-hydroxyethyl) ether, or a poly(ethylene ether) glycolhaving a molecular weight below about 460, including diethylene etherglycol). The comonomer typically can be present in the copolyester atlevels in the range of about 0.5 to about 15 mole %. Isophthalic acid,pentanedioic acid, hexanedioic acid, 1,3-propane diol, and1,4-butanediol are preferred because they are readily commerciallyavailable and inexpensive.

Copoly(trimethylene terephthalate) made from 1,3-propanediol can also beused, in which case the comonomer(s) can be selected from the above list(except the aliphatic diols having 2-8 carbon atoms may be used andethanediol should replace 1,3-propanediol in the list). Thecopolyester(s) can contain minor amounts of other comonomers, and suchcomonomers are usually selected so that they do not have a significantadverse affect on the amount of fiber crimp (in the case of aspontaneously crimpable polyester bicomponent fibers) or on otherproperties. Very small amounts of trifunctional comonomers, for example,trimellitic acid, can be incorporated for viscosity control.

The most preferred class of polymers are nylons. By “nylon” is meant oneor more high molecular weight polyamide(s) which contain an amide repeatlinkage in the polymer backbone. They are generally tough, translucentand semicrystalline polymers, typically processed as a melt. There aretwo main classes of nylon polymers, depending on the regularity of theamide linkages. In one class the formula may be written as:

wherein R is preferably C₅-C₈ alkyl, most preferably (CH₂)₅, and whereinn is preferably about 100 to about 180. In the second class, the formulamay be written as:

wherein R is preferably C₄-C₁₀ alkyl, most preferably (CH₂)₄, R′ ispreferably C₄-C₁₂ alkyl, most preferably (CH₂)₆, and wherein n ispreferably about 40 to about 80. When the R group has 5 carbons, thefirst class shown above is generally referred to as nylon 6, and isprepared by ring opening of caprolactam. When the R group has 4 carbonsand the R′ group has 6 carbons, the second class shown above isgenerally referred to as nylon 6,6, and is made polymerizing adipic acidand hexamethylene diamine. The invention is useful with all nylons, andpreferred are nylon 6, nylon 4,6, nylon 6,6, nylon 6,10, nylon 6,12,nylon 12,12, or their copolymers and blends. Most preferred are nylon 6and nylon 6,6, or blends thereof.

Nylon 6,6 preferably has an Mn of 10,000 or more, preferably has an Mnof 50,000 or less, preferably has Mw of 20,000 or more, and preferablyhas a Mw of 50,000 or less.

The polymer compositions can be made using any technique, provided thatthe composition does not contain substantial amounts of anything thatinterferes with the goals of the invention.

The polymeric compound, also referred to as the “polymeric additive”,has the formula:

or salts thereof, wherein A, B and Q, which may be the same ordifferent, are selected from aliphatic or aromatic substituents. Atleast four carbon atoms separate any two of the shown nitrogen groups. Ris an aliphatic or aromatic group. R is inclusive of hetero atoms suchas nitrogen or oxygen, may be substituted or unsubstituted, and ispreferably an alkyl group of 1-8 carbon atoms, and more preferably analkyl group of 1-4 carbon atoms a is 1 to 5, and n is 3 to about 1,000.Preferably n is up to 100, more preferably up to 20.

It should be understood that the polymeric additive can be polymerconsisting essentially of or consisting of the repeating units shownabove. Alternatively, it can be a polymer containing polymeric additiveunits and other polymeric units. Both types of polymeric additives arepresent in many instances, since when heated most of the polymericadditive will react with polymer or polymer forming compounds to form anew polymeric additive (polymer), while some of the initial polymericadditive remains unreacted. For instance, the composition prior toheating may comprise polyester and polymeric additive, and after heatingsuch a composition may form a combination of polyester, block polymer ofreacted polyester and polymeric additive, and unreacted polymericadditive. As another example additive, caprolactam and polymericadditive can form nylon and polymeric additive comprising nylonrepeating units and polymeric additive repeating units.

It is preferred that four or more carbon atoms separate any two of theshown nitrogen groups, and most preferred that A and/or B comprisealkylene units having at least four carbons separating the nitrogenatoms, to obtain good thermal stability. The alkylene and arylene unitsof A and B may be substituted or unsubstituted, straight or branched,etc., as long as the substituent(s) and branches do not substantiallyinterfere with dyeing or other fiber properties (e.g., the chain maycontain an ether group).

The number of tertiary amines may vary from unit-to-unit and, therefore,a is an average. Thus, a is greater than 1. Preferably, a is about2-about 5.

A, B and Q are preferably selected from alkylene substituents containingfrom 4 to 20 carbons and arylene substituents containing from 6 to 18carbons.

Q is preferably alkylene or arylene, such as phenylene or naphthylene. Qis preferably C₄-C₁₀, more preferably C₄-C₈, alkylene, and is preferablystraight chain alkylene.

A and B are preferably C₄-C₁₀, more preferably C₄-C₈ alkylene, which arepreferably straight chain alkylene.

Preferred for polyester and nylon is R is methyl. Another preferred Rfor nylon and polyester is isobutyl.

Any suitable synthesis may be used to prepare the polymeric additive.The polymeric additive can be prepared by polymerizing (i) the polyamineor polyamine salt and (b) aliphatic and aromatic dicarboxylic acids oresters (e.g., adipic acid, dimethyl adipate, terephthalic acid, dimethylterephthalate, isophthalic acid, dimethyl isophthalate, naphthalenedicarboxylic acid, dimethyl naphthalene dicarboxylate or mixturesthereof, etc., preferably adipic acid, dimethyl adipate, terephthalicacid, dimethyl terephthalate and mixtures thereof). The tertiary amineof the polymeric additive can be partly or completely salinized withphosphorous acid, phosphoric acid, pyrophosphoric acid or phenylphosphinic acid. In a preferred embodiment, the polymeric additive isnot a salt.

When preparing the polymeric additive from a dicarboxylic acid thedicarboxylic acid (e.g., terephthalic acid) can be reacted with alcoholto form a diester (e.g., its analogue—dimethyl terephthalate), and thediester is then reacted with the polyamine or polyamine salt to form thepolymeric compound. In an alternative embodiment, (a) the polyamine orpolyamine salt and (b) dicarboxylic acid are reacted to form thepolymeric compound without forming diester intermediate.

Preferably, the polyamine is selected from those having the formula:

H₂N—A[NR—B]_(a)NH₂

or salts thereof, wherein A and B, which may be the same or different,are selected from aliphatic or aromatic substituents provided that atleast four carbon atoms separate any two nitrogen groups, R is analiphatic or aromatic group, and a is 2 to 5.

More preferably, the polyamine is selected from those having theformula:

H₂N(CH₂)_(x)[NR(CH₂)_(y)]_(a)NH₂

or salts thereof, wherein x and y, which may be the same or different,are 4 to 10, a is 2 to 5, and R is an alkyl group containing 1 to 10carbons in a straight or branched chain. Preferably, a is 2 to 4.Preferred polyamines include dimethyltributylenetetraamine (x=y=4, a=2and R=methyl) or salts thereof, and preferably they are combined with anadipate unit.

Preferred polymeric additives arepoly-alkylimino-bisalkylene-adipamides, -terephthalamides,-isophthalamides, or -1,6-naphthalamides, and salts thereof. Mostpreferred is poly (N,N′-dialkylimino-tri(tetramethylene) adipamide,wherein the alkyl group has one to about four carbon atoms.

The molar ratio of (i) the polyamine containing tertiary amine units and(ii) the one or more other monomer unit is approximately 1:1. It ispreferable to add a slight excess on the order of 1 mole %·10 mole % ofthe polyamine (i) relative to (ii) to promote end capping of thepolymeric additive composition with primary amine unit during synthesis.In this embodiment of the invention, the amine groups on the end of thepolymeric additive molecule are available to form amide linkages withthe polymer component of the composition. An excess of (ii), the one ormore other monomer units, may also be used.

The number average molecular weight (Mn) of the polymeric additive(before reaction with polymer units, such as polyester units or nylonunits) is preferably at least about 1,000, more preferably at leastabout 3,000, and most preferably at least about 4,000, and preferablyabout 10,000 or less, more preferably about 7,000 or less, and mostpreferably about 5,000 or less. The preferred Mn depends on thepolymeric additive used, the balance of the composition and the desiredproperties.

The polyamine, polymeric additive, composition or products madetherewith can be salinized with any acid that stabilizes the amine orprotects the amine group until dyeing is carried out. The acid ispreferably added to the reaction mixture used to form the polymericadditive. Preferred are inorganic acids such as a phosphorus-containingacids, such as phosphorous acid, phosphoric acid, pyrophosphoric acid orphenyl phosphinic acid, most preferably phosphorous acid. However, whenused with polyester compositions, preferably the amount of polymericadditive salinized with phosphorous acid is below 5 mole %, morepreferably below 2 mole %, and is preferably above 1 mole % (wherein themole % is calculated based on the total moles of tertiary amine groupsin the polyamine compound).

When the polymeric additive is to be used with nylon, it is preferableto reduce the amount of phosphorous acid added to the reaction mixturefor the polymeric additive. Since phosphorous acid is a catalyst fornylon polyamidation, a high level of phosphorous acid may cause a risein pack pressure during spinning due to a molecular weight increase.With nylon, preferably the amount of polymeric additive salinized withphosphorous acid is below 1 mole % of the total (based on the totalmoles of tertiary amine groups in the polymeric additive). When used(with nylon), preferably the amount of polymeric additive salinized withphosphorous acid is at least 0.02 mole %, more preferably, at least 0.1mole %, of the total (based on the total moles of tertiary amine groupsin the polymeric additive).

Salinization is normally not necessary, and it is preferred not tosalinize the polymeric additive or polymer composition.

The polymer composition of this invention is inclusive of unreactedpolymer and polymeric additive.

Preferably the polymer composition is prepared by melt blending thepolymeric additive and the polymer. The temperature should be above themelting points of each component but below the lowest decompositiontemperature, and accordingly must be adjusted for any particularcomposition of polymer and polymeric additive. The polymer and polymericadditive may be heated and mixed simultaneously, pre-mixed in a separateapparatus before the heating occurs, or alternately may be heated andthen mixed. Further, the polymer composition may be formed and thenused, or may be formed during use (e.g., by mixing and heating chips orflakes of polymer and polymer additive in an extruder at a fiber or filmmanufacturing facility, or by blending molten polymer and polymericadditive in fiber or film manufacture.) Melt blending is preferablycarried out at about 200 to about 295° C., most preferably about260-about 285° C., depending on the polymer. For polytrimethyleneterephthalate, the preferred temperatures are about 230 to about 270°C., most preferably about 260° C. For polyethylene terephthalate, thepreferred temperatures are about 200 to about 295° C., most preferablyabout 280-about 290° C. For polybutylene terephthalate, the preferredtemperatures are about 200 to about 295° C., most preferably about250-about 275° C. For nylon 6,6, the preferred temperatures are about200 to about 295° C., most preferably about 280-about 290° C. For nylon6, the preferred temperatures are about 200 to about 295° C., mostpreferably about 260-about 275° C.

As noted previously, the polymer and the polymeric additive can react.Since there is more polymer than polymeric additive, the compositioncomprises polymeric additive comprising polymer and polymeric additiverepeat units and unreacted polymer. In many instances it will alsocontain polymeric additive that has no units from the polymer.

When polyester and polymeric additive are reacted, the polymer andpolymeric additive form a block copolymer by reacting at their ends. Byblock copolymer, reference is to a polymer formed by the polyesterjoined to the polymeric additive by a covalent bond. In correspondingnylon compositions, a random copolymer can be formed when the mixingtime is long because of transamidation reactions.

The polymeric additive can also be added to the reactants used to formthe polymer and, then, when the polymer is formed some of the polymerwill contain units derived from polymeric additive. This can result inblock or random polymers being formed with polymeric additive as a unitin the chain.

The polymer composition contains an effective amount of polymericadditive containing a tertiary amine unit to promote acid-dyeability.The particular amount of polymeric additive used depends on thepolyester or nylon compositions; the polymeric additive used,particularly the nature and amount of tertiary amines; the acid dyeused. The preferred amount of polymeric additive can be calculated basedon the amount of tertiary amine of the polymeric additive in thecomposition. Very small amounts of the polymeric additive are neededwhen it is desired to make minor corrections to the dye depth achievedby the polymer. In such instances the composition can contain as littleas about 6 moles tertiary amine/per million grams of the resultingpolymer (mpmg). When more than minor changes are desired, thecomposition preferably contains about 44 or more moles tertiaryamine/per million grams of the resulting polymer (mpmg), even morepreferably about 88 or more mpmg, and most preferably about 132 mpmg ormore, and preferably the composition contains up to about 480 mpmg, morepreferably up to about 322 mpmg and most preferably up to 240 mpmg.

It is believed that when linear polymer forming conditions are employedand the polyester (e.g., polyalkylene terephthalate) or nylon and thepolymeric additive are mixed and heated to form a composition, theprimary amine functional group at the end of the triamine moleculeportion of the polymeric additive reacts to form an amide linkage withcarboxyl groups of the polyester or nylon, leaving the tertiary amineunit portion of the triamine essentially unreacted and free to form adye site. Thus, the tertiary amine units become a part of the polymerchain and their presence in the polymer (e.g., polyester or nylon) fiberformed from the acid-dyeable compositions of the invention is permanentand not easily removed by washing, dry cleaning or other processes usedto launder fabric articles.

The acid-dyeable polymer composition of the invention typically does notdiscolor and/or thermally degrade. This is especially advantageous whenthe polyester or nylon composition is thermally processed, for example,by extrusion from the melt, into shapes such as films, fibers ormembranes. The dyed articles are superior in color fastness, brightness,weather resistance, wear resistance and oxidation stability.

The polyester or nylon composition of the invention may be used toproduce acid-dyeable shaped articles, including high strength shapedarticles. A difficulty is that the use of additives to enhance oneproperty of a polymer, e.g., acid-dyeability, often negatively affectsother properties such as processability and strength. However, inaccordance with the invention, acid-dyeable, high strength nylon fibersare obtained.

Other additives may be added to the acid-dyeable polyester compositionsof this invention to improve strength or facilitate post extrusionprocessing. For example, hexamethylene diamine and/or polyamides such asnylon 6 or nylon 6,6 may be added in minor amounts (e.g., about0.5-about 5 mole %) to add strength and processability.

The polymer composition can, if desired, contain various otheradditives, e.g., antioxidants, delusterants (e.g., TiO₂, zinc sulfide orzinc oxide), colorants (e.g., dyes or pigments), stabilizers, flameretardants, fillers (such as calcium carbonate), antimicrobial agents,antistatic agents, optical brightners, extenders, processing aids,viscosity boosters, toning pigments and other functional additives. TiO₂may be added to the polymer or fibers.

The compositions of this invention are useful in fibers, fabrics, filmsand other useful articles, and methods of making such compositions andarticles. By “fibers”, reference is made to items recognized in the artas fibers, such as continuous filaments, staple, and other choppedfibers. The fibers may be monocomponent (sometimes also referred to as“homofibers”), or bicomponent or other multicomponent fibers, includingsheath-core, eccentric sheath-core, and side-by-side fibers, and yarnsmade therefrom. Fabrics include knitted, woven and nonwoven fabrics. Thecompositions may form a film or a film layer, etc.

The acid-dyeable polyester compositions can be used to make acid-dyeablepolyester bicomponent fibers, for example, bicomponent fibers comprisingpoly(ethylene terephthalate) and poly(trimethylene terephthalate) orpoly(ethylene terephthalate) and poly(tetramethylene terephthalate).Bicomponent fibers based on poly(ethylene terephthalate) andpoly(trimethylene terephthalate) are preferred. The polymeric additivecan be incorporated into either or both components. The components canbe arranged in a sheath-core, eccentric sheath-core, or side-by-siderelationship. When it is desired that the bicomponent fiber be crimpableon drawing, heat-treating, and relaxing to form a stretchable fiber, aneccentric sheath-core or side-by-side relationship can be used;side-by-side is preferred for higher crimp levels. The preferredpolyethylene terephthalate/polytrimethylene terephthalate bicomponentfibers can be manufactured as described in copending U.S. patentapplication Ser. Nos. 09/758,309 (Docket No. LP4440-CIP1), which isincorporated herein by reference. One or both of the polyesters used inthese bicomponent fibers can be copolyesters. Comonomers useful in suchcopolyesters are described previously. The comonomer can be present inthe copolyester at a level in the range of about 0.5 to 15 mole percent.

Acid dyeing is carried out using conventional techniques, such as thoseused for nylon. The polymer compositions, fibers, films, yarns, fabrics,membranes, etc., may be acid dyed.

The polymer composition, or fibers, films, yarns, fabrics, membranes andother useful shaped articles can be acid dyed to a dye exhaustion ofabout 30%-about 90% or higher, preferably about 60%-about 95% or higher.

The acid-dyeable polymer compositions according to the present inventioncontain tertiary amines and are basic compounds. As such, they have arelatively high affinity for acid dyes and can be dyed in a range ofcolors. For example, the acid dyeable polyester compositions may be spuninto fibers and dyed with C.I. Acid Blue 25 (C.I. 62055), C.I. Acid Red4 (C.I. 14710), C.I. Acid Yellow 40 (C.I. 18950), C.I. Acid Green 25(C.I. 61570), Tectonic Yellow 2G, Tectilon Red 2B, Tectilon Blue 4R,Lanaset Yellow 2R, Lanaset Red 2B, Lanaset Blue 2R and Irgalanpremetallized acid dyes either alone or in combination. (These dyes areavailable from Ciba Specialty Chemicals Corporation, High Point, N.C.(Ciba).) Acid dye conditions according to the invention are preferablyfrom a pH of 3.5 or more, and a pH of 4.5 or more is especiallypreferred ranging up to a pH of about 6.5. Of course, lower pH values,e.g., 3.0, may be used if desired.

The invention is further directed to the acid-dyed polymer compositionprepared by acid dyeing any of the acid-dyeable polymer compositionsdescribed above, and to a process comprising (1) providing theacid-dyeable polyester or nylon composition and (2) acid dyeing thecomposition, as well as acid-dyed fibers, film, yarn, fabric, membrane,etc.

TESTING METHODS

Intrinsic Viscosity

Intrinsic viscosity (IV) was determined using viscosity measured with aViscotek Forced Flow Viscometer Y900 (Viscotek Corporation, Houston,Tex.) for the polyester dissolved in 50/50 weight % of trifluoroaceticacid/methylene chloride at a 0.4 grams/dL concentration at 19° C.following an automated method based on ASTM D 5225-92. These measured IVvalues were correlated to IV values measured manually in 60/40 weight %of phenol/1,1,2,2-tetrachloroethane, following ASTM D 4603-96.

DYEING TESTS

A: Tectilon Acid Dyes in the Presence of Carrier

The as-spun yarn was knitted into a sock sample. A 5 gram sock samplewas put into a scouring solution containing 2 weight % Merpol HCSnonionic surfactant (DuPont) and 1 weight % acetic acid at 72° C. for 20minutes. The sample was rinsed and placed into a 100 ml dye-bathcontaining 1 weight % of either Tectilon yellow 2G, Tectilon red 2B orTectilon blue 4R and 0.5% Tanalon HIW carrier (Sybron Chemicals,Birmingham, N.J.) at pH 3. The dye bath was heated to 100° C. for 90minutes. The sample was then rinsed with water and treated with 4%Erional PA solution (Ciba Corporation, Greensboro, N.C.) at pH 4.5-5.0at 82° C. for 20 minutes for dye fixing. The remaining dye solution wasmeasured in a visible spectrometer to calculate the exhaust.

Tectilon acid dyes were also run without a carrier in an identicalmanner to that above.

B: Lanaset Acid Dyes in the Absence of Carrier

The as-spun yarn was knitted into sock sample. A 5 gram sock sample wasput into a scouring solution containing 2% Merpol HCS and 1% acetic acidat 72° C. for 20 minutes. The sample was rinsed and placed into a 100 mldye bath containing 2% of either Lanaset Yellow 2R, Lanaset Red 2B, orLanaset Blue 2R at pH 3. The dye bath was heated to 100° C. for 90minutes. The sample was then rinsed with water and treated with 4%Erional PA solution at pH 4.5-5.0 at 82° C. for 20 minutes for dyefixing. The remaining dye solution was measured in a visible-rangespectrometer to calculate the exhaust.

Tensile Testing of Fiber Yarns

Tensile testing was carried out at 70° F. (21° C.), relative humidity65%, on an Instron type tensile tester. Yarn samples were twisted 3turns per inch and were tested at a crosshead speed of 3.6 inches/minuteat a gauge length of 6 inches. Five samples were run for each itemtested.

EXAMPLES

The following examples are presented for the purpose of illustrating theinvention, and are not intended to be limiting. All parts, percentages,etc., are by weight unless otherwise indicated.

Example 1

N,N′-Dimethyl-N,N′-bis(3-cyanopropyl)-1,4-butanediamine

To a mixture of 14.9 g (0.13 mol) of N,N′-dimethyl-1,4-butanediamine (F.Devinsky, I. Lacko, and L. Krasnec, Synthesis (1980), 303-305) and 50 mLof 6M aqueous sodium hydroxide was added with stirring and cooling 39.9g (0.27 mol) of 4-bromobutyronitrile. The mixture was left standingovernight, then was extracted several times with methylene chloride.Removal of solvent from the combined extracts by rotary evaporation atreduced pressure, followed by molecular distillation at high vacuum,afforded 26.5 g ofN,N′-dimethyl-N,N′-bis(3-cyanopropyl)-1,4-butanediamine (0.11 mol, 83%of theory).

Example 2

Dimethyltributylenetetramine

A 26.5-g portion ofN,N′-dimethyl-N,N′-bis(3-cyanopropyl)-1,4-butanediamine dissolved in 20mL of ethanol was hydrogenated over 1.3 g of Raney Cobalt 2724 for eighthours at 75° C. and 900 psig hydrogen pressure. Following removal ofcatalyst and solvent the product was distilled at ca. 130° C. in amolecular still under high vacuum, affording 24.0 g ofdimethyltributylenetetramine.

The foregoing disclosure of embodiments of the present invention hasbeen presented for purposes of illustration and description. It is notintended to be exhaustive or to limit the invention to the precise formsdisclosed. Many variations and modifications of the embodimentsdescribed herein will be obvious to one of ordinary skill in the art inlight of the above disclosure. The scope of the invention is to bedefined only by the claims appended hereto, and by their equivalents.

What is claimed is:
 1. A polymer having the formula:

or salt thereof, wherein A is defined as equal to B, and as equal to—(CH2)x— where x=4 to 10; R is defined as a C1 to C8 aliphatic group,straight-chain or branched; Q is phenylene, naphthalene, or astraight-chain C4-C10 alkylene; the value of n is in the range of 10 to200; and small “a” is 2 to
 5. 2. The polymer of claim 1 which is not asalt.
 3. The polymer of claim 1 which is a salt.
 4. The polymer of claim3 which is salinized with phosphorous acid, phosphoric acid,pyrophosphoric acid or phenyl phosphinic acid.
 5. The polymer of claim 1prepared by polymerizing (a) polyamine having the formula:H₂N(CH₃)_(x)[NR(CH₂)_(y)]_(a)NH₂ or salts thereof, wherein x and y,which may be the same or different, are 4 to 10, a is 2 to 5, end R isan alkyl group containing 1 to 8 carbons in a straight or branched chainand (b) adipic acid, dimethyl adipate, terephthalic acid, dimethylterephthalate, isophthalic acid, dimethyl isophthalate, naphthalenedicarboxylic acid, dimethyl naphthalene dicarboxylate or mixturesthereof.